Description: Understanding the dynamics and fate of methane (CH 4 ) release from oceanic seepages on margins and shelves into the water column, and quantifying the budget of its total discharge at different spatial and temporal scales, currently represents a major scientific undertaking. Previous works on the fate of methane escaping from the seafloor underlined the challenge in both, estimating its concentration distribution and identifying gradients. In April 2019, the Envri Methane Cruise has been conducted onboard the R/V Mare Nigrum in the Western Black Sea to investigate two shallow methane seep sites at ∼120 m and ∼55 m water depth. Dissolved CH 4 measurements were conducted with two continuous in-situ sensors: a membrane inlet laser spectrometer (MILS) and a commercial methane sensor (METS) from Franatech GmbH. Additionally, discrete water samples were collected from CTD-Rosette deployment and standard laboratory methane analysis was performed by gas chromatography coupled with either purge-and-trap or headspace techniques. The resulting vertical profiles (from both in situ and discrete water sample measurements) of dissolved methane concentration follow an expected exponential dissolution function at both sites. At the deeper site, high dissolved methane concentrations are detected up to ∼45 m from the seabed, while at the sea surface dissolved methane was in equilibrium with the atmospheric concentration. At the shallower site, sea surface CH 4 concentrations were four times higher than the expected equilibrium value. Our results seem to support that methane may be transferred from the sea to the atmosphere, depending on local water depths. In accordance with previous studies, the shallower the water, the more likely is a sea-to-atmosphere transport of methane. High spatial resolution surface data also support this hypothesis. Well localized methane enriched waters were found near the surface at both sites, but their locations appear to be decoupled with the ones of the seafloor seepages. This highlights the need of better understanding the processes responsible for the transport and transformation of the dissolved methane in the water column, especially in stratified water masses like in the Black Sea.

Description: Highlights • Geochemical analyses highlight multiple diagenesis processes occurring in the sediment. • Intense methane seepages and organic matter degradation contribute to the sulfate reduction. • Chemical of dissolved and mineral iron species indicate that iron is associated with clay minerals. • In response to seawater intrusion, ion exchange, dissolution and reverse weathering reactions change the composition of clay constituting the sediment. Abstract Pore water and sediment geochemistry in the western Black Sea were investigated on long Calypso piston core samples. Using this type of coring device facilitates the recovery of the thick sediment record necessary to analyze transport-reaction processes in response to the postglacial sea-level rise and intrusion of Mediterranean salt water 9 ka ago, and thus, to better characterize key biogeochemical processes and process changes in response to the shift from lacustrine to marine bottom water composition. Complementary data indicate that organic matter degradation occurs in the upper 15 m of the sediment column. However, sulfate reduction coupled with Anaerobic Methane Oxidation (AOM) is the dominant electron-accepting process and characterized by a shallow Sulfate Methane Transition Zone (SMTZ). Net silica dissolution, total alkalinity (TA) maxima and carbonate peaks are found at shallow depths. Pore water profiles clearly show the uptake of K+, Mg2+ and Na + by, and release of Ca2+ and Sr2+ from the heterogeneous lacustrine sediments, which is likely controlled by chemical reactions of silicate minerals and changes in clay mineral composition. Iron (Fe2+) and manganese (Mn2+) maxima largely coincide with Ca2+ peaks and suggest a close link between Fe2+, Mn2+ and Ca2+ release. We hypothesize that the Fe2+ maxima below the SMTZ result from deep Fe3+ reduction linked to organic matter degradation, either driven by DOC escaping from the shallow sulfate reduction zone or slow degradation of recalcitrant POC. The chemical analysis of dissolved and solid iron species indicates that iron is essentially associated with clay minerals, which suggests that microbial iron reduction is influenced by clay mineral composition and bioavailability of clay mineral-bound Fe(III). Overall, our study suggests that postglacial seawater intrusion plays a major role in shaping redox zonation and geochemical profiles in the lacustrine sediments of the Late Quaternary.